JP2011020097A - Purification device and method - Google Patents

Abstract

A purification apparatus capable of increasing purification efficiency is provided.
The present invention relates to a purification apparatus for treating impurities with ozone dissolved in liquid Lq. A gas-liquid mixture generation unit S that generates a gas-liquid mixture mixed with the liquid Lq, in which the gas containing ozone becomes nano-sized bubbles B, and the gas-liquid mixture generated by the gas-liquid mixture generation unit S An ozone dissolving part M that breaks down the bubble B of the liquid and dissolves ozone in the liquid Lq. The gas-liquid mixture generator S pressurizes and supplies a gas containing ozone to the liquid Lq so that the concentration of ozone contained in the gas-liquid mixture is equal to or higher than the saturated dissolution concentration of the liquid Lq. Part 1 is provided.
[Selection] Figure 1

Description

  The present invention relates to a purification method and a purification device for purifying an impurity-containing liquid containing impurities such as organic substances.

  Conventionally, purification devices using ozone have been proposed. For example, the purification device described in Patent Document 1 includes a filter, an ozone micro-nano bubble generation water tank, an ozone nano-bubble generation water tank, and an organic sludge decomposition tank. An underwater pump type ozone micro-nano bubble generator and a swirl type ozone micro-nano bubble generator that generate ozone micro-nano bubbles in the water in the nano-bubble generation tank are installed, respectively. An ozone nanobubble generator that generates ozone nanobubbles in water is installed.

  And the water filtered with the filter is introduced into at least one of the ozone micro-nano bubble generation water tank and the ozone nano bubble generation water tank, and at least one of the water containing the ozone micro-nano bubble and the water containing the ozone nano bubble is After being generated, at least one of water containing ozone micro-nano bubbles and water containing ozone nano-bubbles and organic sludge captured by a filter are introduced into the organic sludge decomposition tank, and these water and By stirring the organic sludge with a blower, the organic sludge is changed to inorganic sludge with ozone.

JP 2008-149215 A

  However, the above conventional example has a problem that the amount of ozone micro-nano bubbles and ozone nano-bubbles contained in water is small and the purification efficiency is low.

  This invention is made | formed in view of said point, and it aims at providing the purification apparatus and purification method which can make purification efficiency high.

  The purification apparatus A according to claim 1 of the present invention is a purification apparatus that treats impurities with ozone dissolved in the liquid Lq, and the gas containing ozone is mixed with the liquid Lq as nano-sized bubbles B. The gas-liquid mixture generating part S that generates the gas-liquid mixed liquid, and the ozone dissolving part M that dissolves ozone in the liquid Lq by collapsing the bubbles B of the gas-liquid mixed liquid generated by the gas-liquid mixed liquid generating part S The gas-liquid mixture generation unit S pressurizes the gas containing ozone to the liquid Lq so that the concentration of ozone contained in the gas-liquid mixture is equal to or higher than the saturated dissolution concentration of the liquid Lq. It is characterized by comprising a pressurizing unit 1 to be supplied.

  The purifying apparatus A according to claim 2 of the present invention is the purifying apparatus A according to claim 1, wherein the ozone dissolving part M uses at least one of heating, ultrasonic waves, microwaves, and stirring. The bubble B is collapsed to dissolve ozone in the liquid Lq.

  In the purification method according to claim 3 of the present invention, the concentration of ozone is set to be equal to or higher than the saturated dissolution concentration of the liquid Lq by pressurizing and mixing the gas containing ozone to the liquid Lq so as to become nano-sized bubbles B. The gas-liquid mixed liquid is generated, the bubbles B of the gas-liquid mixed liquid are collapsed, and ozone is dissolved in the liquid Lq, whereby impurities are treated with the dissolved ozone.

  The purification method according to claim 4 of the present invention is the purification method according to claim 3, wherein at least one of heating, ultrasonic waves, microwaves, and stirring is performed when the bubbles B of the gas-liquid mixed solution are collapsed to dissolve ozone in the liquid Lq. One or more means are used.

  The purification method according to claim 5 of the present invention is characterized in that, in claim 3 or 4, the liquid Lq is water.

  The purifying method according to claim 6 of the present invention is the purifying method according to any one of claims 3 to 5, wherein the gas-liquid mixed liquid contains bubbles B in the liquid Lq composed of molecules that form hydrogen bonds. Thus, the hydrogen bond distance of molecules present at the interface of the liquid Lq with the bubble B is shorter than the hydrogen bond distance when the liquid Lq is at normal temperature and pressure.

  The purification method according to claim 7 of the present invention is the purification method according to any one of claims 3 to 6, wherein the liquid Lq is an O—H bond, an N—H bond, a (halogen) —H bond, or an S—H bond. It consists of a molecule | numerator which has any one or more types.

  The purification method according to claim 8 of the present invention is the purification method according to any one of claims 3 to 7, wherein the pressure of the gas forming the bubble B of the gas-liquid mixture is given by the following Young Laplace equation: The pressure is higher than the internal pressure of the bubbles.

Young Laplace's formula ΔP = 2σ / r
[ΔP: rising pressure inside the bubble, σ: surface tension, r: bubble radius]

  In the first aspect of the invention, impurities can be treated with the gas-liquid mixture whose ozone concentration has become higher than the saturated dissolution concentration of the liquid Lq by pressurization of the pressurizing unit 1, and dissolved in the liquid Lq. Purified efficiency such as decomposition and removal of impurities can be increased by the ozone applied.

  In the invention of claim 2, the bubble B can be surely collapsed by the ozone dissolving part M to dissolve ozone in the liquid Lq, and the purification efficiency of impurities in the liquid Lq can be increased by the dissolved ozone. It is.

  In the invention of claim 3, impurities can be treated with a gas-liquid mixed liquid whose ozone concentration is higher than the saturated dissolution concentration of liquid Lq by pressurization, and the impurities are dissolved by ozone dissolved in liquid Lq. It is possible to increase the purification efficiency such as the decomposition and removal of the water.

  In the invention of claim 4, the bubbles B can be collapsed to reliably dissolve ozone in the liquid Lq, and the dissolved ozone can increase the purification efficiency of impurities in the liquid Lq.

  In the invention of claim 5, a gas-liquid mixture can be easily obtained without using a special liquid, and the water molecule is an O ... H hydrogen bond, that is, an oxygen atom of a certain water molecule. Since a strong bond is formed between the hydrogen atom and the hydrogen atom of another water molecule, the hydrogen bond at the bubble interface is strengthened and the bubble B can be further stabilized.

  In the invention of claim 6, since the distance of the hydrogen bond at the bubble interface is shortened, the periphery of the bubble B can be surrounded by liquid molecules that form a strong hydrogen bond, and the liquid molecule that forms the hydrogen bond is strong. Since the bubble B is encased and envelops the bubble B, it does not collapse even if the bubbles B collide with each other, and can counteract the pressure from the liquid Lq by the stress from the inside of the bubble, and the bubble B containing ozone is liquid It can exist stably without disappearing or coalescing in Lq. And since this hydrogen bond is stable over a long period of time, it is possible to obtain a gas-liquid mixture in which bubbles B containing ozone are stably present. In addition, the bubbles B containing nano-order size ozone can be generated at a density far exceeding the conventional level and can be stably present in the liquid Lq.

  In the invention of claim 7, since the liquid Lq is a liquid composed of molecules having any one or more of OH bond, NH bond, (halogen) -H bond, and SH bond, these The bond is a bond between a hydrogen atom and an atom having a sufficiently large electronegativity relative to a hydrogen atom, such as OH ... O, NH ... N, F-H ... F, Cl-H ... Cl, and the like. A strong hydrogen bond such as (halogen) -H (halogen), S—H... S is formed, and the bubble B can be stabilized by surrounding the bubble by the hydrogen bond.

  In the invention of claim 8, when the internal pressure of the bubble B becomes a pressure given by the Young Laplace formula, the bubble B is maintained at a high internal pressure, and a stronger interface structure can be formed. It is possible to form a stable bubble B in the installed state.

It is the schematic which shows an example of embodiment of the purification apparatus of this invention. An example of the ozone dissolution part same as the above is shown, and (a) and (b) are schematic views. It is the schematic which shows an example of a pressurization part same as the above. (A)-(c) is the schematic which shows a part. (A)-(d) is the schematic which shows a part. It is the schematic which shows a part same as the above. It is the schematic which shows an example of the purification method of this invention. It is a schematic diagram same as the above. It is a schematic diagram same as the above. It is the schematic which shows the other example of embodiment of the purification apparatus of this invention. (A) is the schematic which shows the other example of embodiment of the purification apparatus of this invention, (b) is the schematic which shows a prior art example. It is a graph which shows the difference of the infrared absorption spectrum of the gas-liquid liquid mixture using ozone containing nitrogen and water, and ozone containing nitrogen saturated water. It is a graph which shows the gas volume contained in a gas-liquid liquid mixture. It is a photograph of the gas-liquid mixed solution by a scanning electron microscope (SEM). It is a conceptual explanatory drawing of the gas-liquid interface of the bubble in a gas-liquid mixed liquid. It is a graph which shows stability of a gas-liquid liquid mixture. In Example 2, it is a graph which shows a time-dependent change of the density ^| concentration of Fe2 ⁺ .

  Hereinafter, modes for carrying out the present invention will be described.

  As shown in FIG. 1, the purification device A of the present invention includes a gas-liquid mixed liquid generation unit S and an ozone dissolution unit M. The gas-liquid mixture generation unit S is an apparatus that continuously pumps the liquid Lq to produce a gas-liquid mixture, and takes out the liquid Lq held at atmospheric pressure (0.1 MPa) from the liquid reservoir 12 and pumps it. Pressurizing unit 1 for pressurizing, gas supplying unit 2 for supplying a gas containing ozone to pressurized liquid Lq, and gas-liquid mixing unit for making the supplied gas into fine bubbles and mixing with liquid Lq 3, a defoaming part (gas-liquid separation tank) 4 for removing large bubbles present in the gas-liquid mixed liquid in the gas-liquid mixing part 3, and a gas-liquid mixed liquid from which large bubbles are removed by the degassing part 4 A pressure reducing section 5 that gradually reduces the pressure to atmospheric pressure without generating large bubbles and a discharge section 7 that discharges the decompressed gas-liquid mixed liquid are provided. ing.

  The pressurizing unit 1 pumps the liquid Lq to the gas-liquid mixing unit 3 and can be constituted by, for example, a pump 11 that sucks up the liquid Lq from the liquid storage tank 12 as in this device.

  The gas supply unit 2 is connected to the flow path 6 to supply a gas containing ozone to the liquid Lq. For example, an ozone generator 2b and a pressure regulating valve 2c are provided on the ozone injection pipe 2a. The ozone generator 2b is provided closer to the flow path 6 than the pressure regulating valve 2c. As the ozone generator 2b, for example, ozone is generated by electric discharge from oxygen in the air taken in from the suction port 2d. Can be used. In addition to forming the ozone injection part 2 using such an ozone generator 2b, the ozone injection part 2 can be formed by supplying ozone from a cylinder filled with ozone. The connection position of the ozone injection part 2 to the flow path 6 may be a position upstream from the gas supply part 3 and is connected to the flow path 6 upstream from the pressurization part 1 as shown in FIG. Alternatively, it may be either connected to the flow path 6 on the downstream side of the pressurizing unit 1.

  The gas-liquid mixing unit 3 mixes the liquid Lq sent under pressure and the gas injected into the liquid Lq, and makes the gas into fine bubbles by pressurization to disperse and mix in the liquid Lq. The gas-liquid mixing unit 3 can be configured to give a stirring force by changing the cross-sectional area of the flow path or the like, and if the liquid Lq is flowing in the flow path 6 with stirring, the flow is simply flowed. It can also be constituted by a path 6. When the gas supply unit 2 is in the flow path 6 on the upstream side of the pressurizing unit 1 as in this apparatus, the pressurizing unit 1 constituted by the pump 11 or the like may also be used as the gas-liquid mixing unit 3. When pressurization and mixing of gas and liquid are performed by the pump 11, the liquid Lq can be rapidly pressurized and mixed, so that a gas-liquid mixture having a strong structure at the bubble interface can be reliably generated. Moreover, it is also preferable that the gas-liquid mixing unit 3 is constituted by a Venturi tube. In that case, the liquid can be rapidly pressurized and mixed with a simple configuration. In the gas-liquid mixing unit 3, the liquid and the gas are mixed under high pressure conditions. Thereby, a strong interface structure is formed around the bubble B, the bubble B can be covered with the shell of the strong interface structure, and the gas can be stabilized as a fine bubble.

By the pressurization unit 1 and the gas-liquid mixing unit 3 as described above, a strong pressure is suddenly applied to the liquid into which the gas is injected, and the bubbles existing in the liquid are subdivided into fine nano-sized bubbles. And dispersed in the liquid. In addition, a strong interface structure is formed by liquid molecules at the interface of the bubbles that have become high pressure due to a sudden pressure change. At that time, when the pressurization rate ΔP ₁ / t (ΔP ₁ : pressure increase, t: time) is 0.17 MPa / sec or more, the bubbles are subdivided to generate fine nano-sized bubbles. Nano-sized bubble B in which the interface of the bubble B has a strong structure when the pressure of the gas-liquid mixed solution when being sent out from the gas-liquid mixing unit 3 to the defoaming unit 4 becomes 0.15 MPa or more. Can be generated. In consideration of substantial pressurization conditions, the upper limit of the pressurization rate ΔP ₁ / t is 167 MPa / sec, and the upper limit of the pressure of the pressurized gas-liquid mixture is 50 MPa.

  FIG. 3 is a schematic view of a main part showing an example of a specific form of the pump 11. The pump 11 a pressurizes the liquid by the rotation of the rotating body 21, and the rotating blades 22 attached to the rotating body 21 continuously rotate to pump the pump outlet 27 through the pump passage chamber 23 from the pump inlet 26. The liquid is sent out in the direction of flow to and pressurized. In the figure, the white arrow indicates the flow direction of the liquid, and the solid line arrow indicates the rotation direction of the rotating body 21. The pump 11a includes four rotary blades 22. Further, the rotating shaft 25 of the rotating body 21 is arranged so as to be deviated toward the pump outlet 27 side from the cylindrical center of the pump wall 24 formed in a cylindrical shape, and is provided as an eccentric shaft. The volume of the second flow path chamber 23b of the pump flow path chamber 23 is formed smaller than the volume of the first flow path chamber 23a due to the eccentricity of the rotary shaft 21, and the pump flow path chamber is arranged along the liquid flow direction. The volume of 23 is gradually reduced.

Then, the liquid fed to the pump flow passage chamber 23 is pressurized is fed by rotating blades 22, large bubbles B _B due to rapid pressure changes bubbles B _N of subdivided by fine nano-sized generated . That is, the liquid sent from the first flow path chamber 23a to the second flow path chamber 23b along with the rotation of the rotating body 21 is rapidly compressed and pressurized as the volume of the pump flow path chamber 23 becomes smaller. Nano-sized bubbles _BN are generated by the pressure. Further, in the illustrated pump 11a, a shearing force is applied when the liquid passes between the inner surface of the pump wall 24 and the tip of the rotor blade 22, and the liquid is pressurized while being sheared by the clearance. At this time, the gas (large bubbles B _B ) mixed in the liquid is sheared by the shearing force applied to the liquid and becomes finer nano-sized bubbles (B _N ). The distance narrowest part between the inner surface of the pump wall 24 and the tip portion of the rotor blades 22, i.e. the clearance distance L _C is preferably 5Myuemu～2mm. Thus, according to the pump 11a using the rotator 21, it is possible to form nano-sized bubbles by shearing the gas injected into the liquid while being rapidly pressurized with the rotator 21 with a strong force. A gas-liquid mixture having a strong bubble interface structure can be generated more reliably.

  The rotational speed of the rotating body 21 of the pump 11 is preferably 100 rpm or more. At this time, it becomes 1/2 rotation or more in 0.3 seconds. By having such a rotational speed, it is possible to reliably generate nano-sized bubbles in which the hydrogen bond distance is shortened by injecting a gas having a saturation dissolution concentration or more into the liquid.

  The pressurization by the pressurizing unit 1 and the gas-liquid mixing unit 3 can be performed multiple times by providing a plurality of pressurizing units 1 or gas-liquid mixing units 3. By pressurizing the liquid a plurality of times while feeding the liquid, the pressurization can be performed by a plurality of pumps 11 and venturi pipes, and the liquid is strongly pressurized to generate a gas-liquid mixture having a strong bubble interface structure. It is something that can be done. Specifically, the pressurizing unit 1 can be composed of a pump 11 and the gas-liquid mixing unit 3 can be composed of one or two or more pumps 11 or Venturi tubes.

  The defoaming section 4 is for removing bubbles exceeding nanosize, that is, bubbles exceeding 1 μm in diameter, from the liquid in which the gas is mixed as described above. The bubbles are lifted by their own buoyancy and removed. It can be composed of a tube or the like. Since the removed bubbles become gas and accumulate on the upper part, the removed gas can be removed by the gas removing unit 8. Bubbles of a size exceeding 1 μm in diameter (micro-sized bubbles) are raised by buoyancy, so that relatively large bubbles are removed and nano-sized bubbles that are fine bubbles are present in the liquid. It is possible to obtain a stable gas-liquid mixture having a strong interface structure.

  Specifically, the defoaming portion 4 can be configured as shown in FIG. (A) is formed so as to be substantially horizontal to the ground surface (on a plane substantially perpendicular to the direction of gravity) continuously with the gas-liquid mixing unit 3, and the bubbles B in the liquid Lq are It shows an example of a tubular body that is lifted up to remove bubbles B. (B) is formed so that the shape combined with the gas-liquid mixing unit 3 and the gas-liquid mixing unit 3 is a reverse L-shape when viewed from the front, and the flow direction of the liquid Lq is downward (the direction of gravity) In this example, the bubbles B are removed by raising the bubbles B in the liquid Lq to the liquid level by the buoyancy. Further, (c) is separated from the gas-liquid mixing unit 3, and the flow direction of the liquid Lq is set downward (substantially the same direction as the direction of gravity), and the bubbles B in the liquid Lq are raised to the liquid level by the buoyancy. This shows an example of a tubular body that is made to remove bubbles B. The bubble gas removed by the defoaming section 4 is returned to the gas supply section 2 by the ozone injection pipe 2a connected to the defoaming section 4, and is used again as a gas containing ozone. It is safe because it is not discharged outside, and it is economical because there is no loss of gas containing ozone.

The decompression unit 5 gradually reduces the pressure of the liquid mixed with gas to atmospheric pressure without generating large bubbles. When the liquid mixed with gas by pressurization as described above is in a high-pressure state and is discharged to the outside under atmospheric pressure as it is, bubbles in the gas-liquid mixture are combined due to a sudden pressure drop. May become a gas and be discharged from the liquid, and cavitation may occur. Therefore, the decompression unit 5 is provided, and when the gas-liquid mixture in a pressurized state is sent out, the decompression unit 5 gradually reduces the pressure to atmospheric pressure and then discharges it. The decompression unit 5 is configured to decompress while reducing the upper limit of the decompression speed ΔP ₂ / t (ΔP ₂ : decompression amount, t: time) over the entire piping while sending a liquid in which gas is mixed. ing. Thus, the gas-liquid mixture can be taken out without erasing or coalescing the nano-sized bubbles while maintaining the structure of the strong bubble interface.

The decompression section 5 can be configured as shown in FIG. 5, and specifically, the flow path 6 in which the cross-sectional area of the flow path gradually decreases as shown in FIG. In this way, the flow path 6 in which the cross-sectional area of the flow path gradually decreases gradually, or the gas-liquid mixing in the high pressure state (P ₁ ) due to the pressure loss in which the pressurized liquid flows in the flow path 6 as in (c) The flow path 6 whose flow path length (L) is adjusted so as to reduce the pressure of the liquid gradually (P ₂ , P ₃ ,...) To the atmospheric pressure (P _n ), and (d) Thus, it can be constituted by a plurality of pressure regulating valves 9 provided in the flow path 6.

For example, when the decompression section 5 as shown in FIG. 5A or 5B is used, the flow path 6 upstream of the decompression section 5 has an inner diameter of 20 mm, and the decompression section 5 has a flow path length of about 1 cm. -10 m, and the inner diameter can be gradually reduced from 20 mm to 4 mm, whereby the cross-sectional area of the channel can be reduced. In addition, the decompression part 5 can be set to inlet inner diameter / outlet inner diameter = about 2-10, or the inner diameter reduction | decrease value per cm can be set to about 1-20 mm. At this time, if the gas-liquid mixed solution is sent to the decompression unit 5 at a flow rate of 4 × 10 ⁻⁶ m / s or more, the decompression rate is 2000 MPa / sec or less and the pressure can be reduced by 1.0 MPa without erasing the nano-sized bubbles. The gas-liquid mixture can be depressurized to atmospheric pressure.

  The discharge unit 7 discharges the decompressed liquid Lq to the liquid storage tank 12. In addition, as shown in FIG. 6, the extension flow path 10 can also be provided between this discharge part 7 and the pressure reduction part 5 in order to ensure sufficient pushing pressure of the liquid in the pressurization part 1. As shown in FIG. That is, the total pressure loss including the decompression unit 5 is calculated, the pressure required to pressurize the liquid and gas in the gas-liquid mixing unit 3 by the indentation pressure from the pressurization unit 1, and the total pressure loss The extended flow path 10 may be added to the flow path 6 with the flow path length adjusted so that the pressure loss of this difference occurs. In order to secure the indentation pressure, it may be possible to provide a throttling portion or the like. However, if the indentation pressure is adjusted by the throttling portion or the like, bubbles may collapse due to a sudden pressure change. However, if the extension channel 10 is provided in this way, the gas-liquid mixture can be discharged while the bubbles are stabilized.

  The ozone dissolving part M is for dissolving bubbles in the liquid Lq by collapsing bubbles of the gas / liquid mixed liquid generated by the gas / liquid mixed liquid generating part S. For example, as shown in FIG. A heater M1 for heating the liquid mixture to a temperature higher than normal temperature can be used. In addition, as shown in FIG. 2 (a), a wave generator M2 for supplying ultrasonic waves and microwaves to the gas-liquid mixture to vibrate, or as shown in FIG. 2 (b), gas-liquid mixing. A stirrer M3 for mechanically stirring and vibrating the liquid by rotation or the like can be used as the ozone dissolving part M. The ozone dissolving part M can be provided at the bottom of the liquid storage tank 12.

Then, when the liquid Lq is purified by decomposing or removing impurities contained in the liquid Lq with the above-described purification device, the following process is performed. First, a gas / liquid mixture is generated by the gas / liquid mixture generation unit S. That is, the liquid Lq is pumped by the pressurizing unit 1, and a gas containing ozone is supplied and injected into the pumped liquid Lq by the gas supply unit 2. Then, the liquid Lq into which the gas has been injected is added by the pressurizing unit 1 and the gas-liquid mixing unit 3 at a pressurization rate ΔP ₁ / t (ΔP ₁ : pressure increase amount, t: time) of 0.17 MPa / sec or more. The liquid pressure is adjusted to 0.15 MPa or more. That is, the pressure of the liquid when being sent out from the gas-liquid mixing unit 3 to the defoaming unit 4 is 0.15 MPa or more. Thereafter, after removing bubbles exceeding the nano size in the gas-liquid mixture in the degassing part 4, a pressure reduction rate ΔP having a maximum pressure reduction rate of 2000 MPa / sec or less while sending the liquid to the pressure reduction part 5 and the downstream flow path 6. _The pressure is gradually reduced to atmospheric pressure at ₂ / t (ΔP ₂ : reduced pressure amount, t: time). Then, by discharging the decompressed gas-liquid mixed liquid from the discharge unit 7 to the liquid storage tank 12, it is possible to generate a gas-liquid mixed liquid in which nano-sized bubbles are stably present. The flow path 6 on the downstream side of the gas-liquid mixing unit 3 can be formed in a tube having an inner diameter of about 2 to 50 mm. As a result, the gas-liquid mixture can be discharged with a relatively thick channel cross-sectional area, and the clogging of the pipe as in the case where the channel 6 is configured by a narrow path can be prevented, and the gas-liquid mixture can be used. It can be made easier.

  After preparing the gas-liquid mixed solution in this way, as shown in FIG. 7, the bubbles B in the gas-liquid mixed solution are collapsed by the ozone dissolving part M to dissolve the ozone in the bubbles in the liquid Lq. Thereby, radicals such as hydroxy radicals (.OH) are generated by the dissolved ozone, and the radicals or ozone itself is allowed to act on the impurities F contained in the liquid Lq to decompose or remove the impurities F. The liquid Lq can be purified. In the present invention, a large amount of ozone can be dissolved by instantaneously collapsing bubbles in the ozone dissolving part M, and the purification concentration can be increased by increasing the concentration of ozone dissolved in the liquid Lq.

  Here, the impurity F is contained in the initial liquid Lq used when preparing the gas-liquid mixture in the gas-liquid mixture generation unit S, and the gas-liquid mixture is generated in the gas-liquid mixture generation unit S. After the preparation, before mixing bubbles in the gas-liquid mixture (liquid Lq) before collapsing bubbles in the ozone dissolution part M, and after the bubbles in the gas-liquid mixture liquid are collapsed in the ozone dissolution part M, the gas-liquid mixture liquid Any of the cases of mixing with (liquid Lq) may be used. In addition, the present invention can be used to decompose and purify organic impurities F contained in septic tanks, sewers, industrial effluents and the like. In the present invention, sludge in biological treatment or activated sludge method is used as impurities F, and the sludge can be decomposed to reduce the amount thereof. Furthermore, the present invention can purify water by oxidizing and recovering metal ions contained in water by ozone. Further, the present invention can purify a liquid containing a harmful substance such as an organic solvent such as benzene, toluene, ethylenebenzene, and xylene as the impurity F by decomposing the impurity and detoxifying it. In addition, as shown in FIG. 8, the present invention can be used to purify a polymer solution containing a polymer having a double bond such as polyvinyl alcohol as an impurity. Furthermore, as shown in FIG. 9, the present invention purifies a solution containing an aromatic compound containing a benzene ring (such as a thermosetting resin) as an impurity by decomposing the double bond of the benzene ring. Can do. Moreover, this invention can be used also as a water purification plant or a rainwater purification apparatus.

  The purification apparatus A shown in FIG. 10 is formed by providing a preliminary mixing tank 50 in addition to the one shown in FIG. A stirring bar 51 is provided at the bottom of the preliminary mixing tank 50. In this purification device, after the water Ls containing soil is preliminarily stirred in the preliminary mixing tank 50, the soil-containing water Ls is put into the liquid storage tank 12 and mixed with the gas-liquid mixture, and the bubbles are collapsed in the ozone dissolving part M. To dissolve ozone in the liquid Lq. Thereby, the metal ion contained in the soil can be oxidized with ozone to deposit and collect the metal and to purify the soil-containing water Ls.

In the purification apparatus A shown in FIG. 11 (a), the liquid storage tank 12 is provided with an ultraviolet lamp (UV lamp) 52 and an activated carbon purification part 53, and the other configuration is shown in FIG. Is equivalent to In the purification apparatus A shown in this figure, the configuration other than the liquid storage tank 12 in FIG. 1 is shown as the apparatus main body S ′, and the ozone dissolution unit M is not shown. In this purification device A, the gas-liquid mixed solution and the wastewater containing impurities are mixed in the liquid storage tank 12 in the same manner as described above, and the wastewater is purified by the dissolved ozone. Is lit in the liquid storage tank 12 so that wastewater can be sterilized or impurities can be decomposed with hydroxy radicals generated by the reaction of H ₂ O ₂ generated by ultraviolet rays or this H ₂ O ₂ with ozone. Then, the waste water is passed through the activated carbon 53a of the activated carbon purification unit 53, so that impurities in the waste water can be removed and purified by the adsorption action of the activated carbon 53a, and the purification efficiency can be increased. .

Conventionally, as shown in FIG. 11B, a purification device provided with ozone and an ultraviolet lamp 52 has been proposed. The purification device, the ozone gas generated in the ozone generator 60 was supplied with aeration in the reaction vessel 61, which is dissolved in the following conditions the saturation concentration in the waste water, after which the H ₂ O ₂ by using an ultraviolet lamp 52 The H ₂ O ₂ and dissolved ozone react with each other to generate hydroxy radicals (.OH). Then, the impurities are decomposed into water, CO _{2 and the} like by the reaction between the hydroxyl radical and the organic substance that is the impurity. In this case, since the solubility (concentration) of ozone in the wastewater decreases with the reaction, ozone gas is continuously supplied and a plurality of reaction tanks 61 are provided to sequentially distribute the wastewater to improve the reaction rate. ing. However, in the present invention, a large amount of ozone can be dissolved by instantaneously collapsing bubbles in the ozone dissolving part M, and the purification concentration can be increased by increasing the concentration of ozone dissolved in the liquid Lq. .

In the purification apparatus A shown in FIG. 1, not only air but also gaseous impurities such as exhaust gas, toxic gas, carbon monoxide, and odor gas can be taken in together with air from the suction port 2d of the ozone injection pipe 2a. . In this case, bubbles in the gas-liquid mixture are filled with ozone and gaseous impurities. And after producing | generating a gas-liquid mixed liquid like the above, a bubble is collapsed by the ozone melt | dissolution part M, ozone is melt | dissolved in the liquid Lq, At the same time, a gaseous impurity is dissolved in the liquid Lq. The exhaust gas is detoxified by the reaction of NO → NO ₂ , the carbon monoxide is detoxified by the reaction of CO → CO ₂ , and the odor gas is detoxified by the reaction of H ₂ S + O ₃ → S + H ₂ O + O ₂ . The surrounding air can be purified.

  In the present invention, as the liquid Lq, it is preferable to use a liquid composed of molecules that form hydrogen bonds. In this case, the distance between the hydrogen bonds of the molecules present at the interface with the bubbles of the liquid is determined as follows. It is preferably shorter than the distance of hydrogen bonding at 25 ° C. and 1 atm (0.1013 MPa). A hydrogen bond is a bond that stabilizes the system in a molecule that has a high electronegativity atom and a hydrogen atom, because the hydrogen atom approaches the high electronegativity atom of another molecule. . In this way, when the gas-liquid mixture exists under normal temperature and normal pressure conditions, the hydrogen bond distance at the bubble interface of bubbles containing ozone becomes shorter than the normal hydrogen bond distance at normal temperature and normal pressure. The bubbles are surrounded by liquid molecules that form strong hydrogen bonds. And the liquid molecule which formed this hydrogen bond turns into a firm shell, and encloses a bubble. As a result, even if the bubbles collide with each other, they will not collapse, and the pressure from the liquid can be countered by the stress from the inside of the bubbles, so that the bubbles containing ozone disappear or merge in the liquid. It can be held without any problems. In other words, it is different from conventional bubbles that are stable with surface tension.

  The distance between the hydrogen bonds of the liquid molecules at the interface with the bubbles can be appropriately set depending on the liquid used, but is 99% or less when the distance between hydrogen bonds at room temperature and normal pressure is 100%. Is preferred. When the hydrogen bond distance falls within this range, the bubbles can be surrounded and stabilized by a hard shell of hydrogen bonds. If the distance between hydrogen bonds is longer than this, there is a possibility that bubbles cannot be stabilized and exist. Considering the interatomic distance, the lower limit of the hydrogen bond distance is 95%. The hydrogen bond distance at the bubble interface in the gas-liquid mixture can be calculated, for example, by analyzing the infrared absorption spectrum (IR) of the liquid in which the bubbles are mixed, as shown in the examples described later. .

  By the way, a liquid having a hydrogen bond distance of the above-mentioned distance usually has a solid or hydrate crystal structure like ice. However, in the above-mentioned liquid, hydrogen having a short distance locally at the bubble interface. Bonds are formed and normal hydrogen bonds are formed in other liquids. That is, a hard shell of liquid molecules is formed by hydrogen bonds at a short distance at the bubble interface to prevent the bubbles from coalescing and disappearing, and at other than the bubble interface, liquid exists in a normal state and normal temperature At normal pressure, fluidity is ensured, and it is easy to use liquid in which stable bubbles are present.

  The bubbles contained in the liquid are nano-sized bubbles, specifically, bubbles having a diameter of 1 to 1000 nm (so-called nano bubbles). When the bubbles are nano-sized and fine, a strong bubble interface structure can be formed, and a high-concentration gas can be held in the liquid. Further, since buoyancy does not act on the nano-order size bubbles, the bubbles do not rise and separate from the liquid, so that the bubbles can exist stably over a long period of time. Even if the bubble is smaller or larger than this range, the bubble may not be stabilized. In addition, the bubble size can be measured by a scanning electron microscope (SEM), and the average particle diameter of the bubbles can be obtained by averaging the particle diameters of the bubbles obtained by the measurement. By the way, the liquid mixed with microbubbles is cloudy and can be discriminated visually. However, the liquid mixed with nanobubbles is colorless and transparent (or the color of the liquid when the liquid is colored) and can be discriminated visually. Can not. Therefore, discrimination of nano-sized bubbles is performed by SEM or density measurement.

  One of the liquids preferably used is water. In this case, the water molecule is a hydrogen bond of O ... H, that is, a hydrogen bond is formed between an oxygen atom of one water molecule and a hydrogen atom of another water molecule, and when water is used as a liquid, This hydrogen bond in the liquid becomes strong at the bubble interface, and the gas bubbles containing ozone can be further stabilized. Further, since water is abundant in supply sources and can be obtained stably, a gas-liquid mixture can be easily obtained without using a special liquid. That is, the water used for the gas-liquid mixture is not limited to high-purity water, and any water can be used, including water and sewage systems, ponds, seawater, and the like. That is, any material that contains water as a liquid may be used.

Further, the liquid is a liquid composed of molecules having any one or more of (halogen) -H bond and S—H bond such as O—H bond, N—H bond, F—H bond and Cl—H bond. It is also preferable. These bonds are bonds between atoms and hydrogen atoms having a sufficiently large electronegativity with respect to hydrogen atoms, such as OH ... O, NH ... N, FH ... F, and Cl-H ... Cl. (Halogen) -H (Halogen), S—H,... S, and so on, are formed, and by this hydrogen bond, bubbles can be surrounded and stabilized. A typical liquid having an O—H bond is water, but other examples include hydrogen peroxide, alcohols such as methanol and ethanol, and glycerin. Moreover, ammonia etc. can be illustrated as a liquid which has a N-H bond. Examples of those having a (halogen) -H bond include HF (hydrogen fluoride) having an F-H bond and HCl (hydrogen chloride) having a Cl-H bond. Examples of those having an S—H bond include H ₂ S (hydrogen sulfide).

  It is also preferable that the liquid is a liquid composed of molecules having a carboxyl group. The carboxyl group has a carbonyl oxygen atom with high electronegativity, and the carbonyl oxygen atom in one carboxyl group and a hydrogen atom in another carboxyl group form a strong hydrogen bond to surround the bubble. Therefore, it is possible to obtain a gas-liquid mixture in which bubbles are stably present. Examples of the liquid composed of molecules having a carboxyl group include carboxylic acids such as formic acid and acetic acid.

  The concentration of ozone contained in the liquid is equal to or higher than the saturated dissolution concentration of ozone in the liquid. By maintaining a saturated dissolved amount or a large amount of ozone exceeding the saturated amount in the liquid, high concentration ozone contained in the liquid can be used, and purification efficiency can be improved. More preferably, a saturated dissolved amount of ozone is dissolved in the liquid, and gas bubbles containing ozone are present in the saturated dissolved solution. If ozone is dissolved in a saturated dissolution amount, it becomes possible to stabilize the ozone in the form of bubbles without dissolving them and hold them as bubbles in the liquid. In other words, in a liquid in which gas is present at a saturation dissolution amount or more, ozone is dissolved at a saturated concentration in the liquid, and the bubbles do not collapse or dissolve. It can be present in the liquid. Furthermore, it is preferable that the ozone dissolution concentration is a saturated dissolution concentration. Thus, when the ozone concentration is high, the bubbles can be stabilized with the hydrogen bond distance shortened, and the ozone is dissolved in the liquid when the stabilized bubbles are subjected to heat or impact. Therefore, the purification efficiency can be further improved. The amount of gas in the liquid can be calculated from the amount of mass change by separating the gas from the liquid as shown in the examples described later.

  The pressure of the gas forming the bubbles, that is, the internal pressure of the bubbles is preferably 0.12 MPa or more, and more preferably higher than the internal pressure of the bubbles given by the Young Laplace equation (the following equation).

Young Laplace's formula ΔP = 2σ / r
[ΔP: rising pressure from the atmospheric pressure inside the bubble, σ: surface tension, r: bubble radius]
When the internal pressure of the bubbles becomes such a pressure, the bubbles are maintained at a high internal pressure, and a stronger interface structure can be formed. Therefore, stable bubbles can be formed in a stationary state. Further, since the internal pressure is higher than the internal pressure of the bubble due to the surface tension given by the Young Laplace equation, more ozone can be stably trapped inside the bubble. On the other hand, once an impact or heat is applied to the liquid, the interface structure of the bubbles collapses due to the force of the internal pressure, and the bubbles coalesce and dissolve ozone, so this ozone can be purified. is there. The internal pressure of the bubbles can be calculated by fitting the total amount of gas in the liquid and the gas volume calculated from the density to the gas equation of state as shown in the examples described later. Note that a liquid in which nano-sized bubbles are mixed has a negative zeta potential when water is used as the liquid, and the area of the bubble interface existing in a volume of 1 cm ³ is about 0.6 m ² .

  Hereinafter, the present invention will be described specifically by way of examples.

  The gas-liquid mixed liquid was produced | generated using the pure water as the liquid Lq with the purification apparatus of FIG.

  As the purification device, a device in which the pressurizing unit 1 and the gas-liquid mixing unit 3 are combined with a pump 11 was used. As the pump 11, a pump 11a as shown in FIG.

The ratio of gas to liquid (the amount of gas injected into the liquid) was set to 1: 1 as a volume ratio (volume ratio). Moreover, the rotation speed of the rotary body 21 of the pump 11 was set to 1700 rpm. Under this condition, gas is injected into water at atmospheric pressure (0.1 MPa) and then pressurized at a pressure rate ΔP ₁ /t=28.3 MPa / sec. The pressure of the liquid at the time of delivery became 0.6 MPa. Under such conditions, it is considered that the gas is injected into the liquid exceeding the saturated dissolution concentration, the hydrogen bond distance is shortened, and a strong bubble interface structure is formed. This condition (pressurizing condition) is considered to be the best condition at present.

  In addition, the flow path 6 on the upstream side of the decompression unit 5 has an inner diameter of 20 mm. As the decompression unit 5, one having an inner diameter that gradually decreases in three stages as shown in FIG. 5A is used. Specifically, the inner diameter is 14 mm, 8 mm, 4 mm, and each length is about 3.3 mm (decompression). The total length of the part 5 was approximately 1 cm) and was composed of three flow path pipe parts. In addition, a hose having an inner diameter of 4 mm (outer diameter of 6 mm) is used as the flow path 6 and the extension flow path 10 on the downstream side of the decompression unit 5, and the combined length of the downstream flow path 6 and the extension flow path 10 is as follows. It was set to be 2 m. Under these conditions, in the decompression section 5, the liquid mixed with the gas is decompressed at a maximum decompression speed of 60 MPa / sec for a time of 0.0025 seconds, and further, 1 MPa / sec for a time of 0.5 MPa in the downstream flow path 6. The liquid in which the gas was mixed in seconds was depressurized, and a gas-liquid mixed liquid depressurized to atmospheric pressure (0.1 MPa) was obtained from the discharge portion 7 which is the tip of the hose. Note that, under such conditions, a gas-liquid mixed liquid in which gas is injected into the liquid exceeding the saturated dissolution concentration and the hydrogen bond distance is shortened and the structure of the bubble interface is strengthened can be stably generated. It is considered a thing. This condition (decompression condition) is considered to be the best condition at the present time.

[Physical properties]
Next, the physical properties of the gas-liquid mixture of Example 1 will be described.

[Hydrogen bond distance]
FIG. 12 is a graph showing a difference between an infrared absorption spectrum of a gas-liquid mixed solution using nitrogen as a gas and pure water as a liquid and a gas saturated solution in which nitrogen is dissolved in pure water at a saturated dissolution concentration. is there. It is known that the infrared absorption band due to the OH contraction vibration of water usually has an absorption maximum in the vicinity of 3400 cm ⁻¹ , but as shown in the graph, the gas-liquid mixture has an absorption maximum of OH contraction vibration of 3200 cm ^−. It is shifted to around ¹ . When the absorption maximum is 3400 cm ⁻¹ , the hydrogen bond distance is 0.285 nm. On the other hand, when the absorption maximum is 3200 cm ⁻¹ , the hydrogen bond distance is known to be 0.277 nm, which is shorter than the normal hydrogen bond distance under normal temperature and pressure, and is structured ice or hide. It was concluded that the water was close to the rate. Therefore, if ozone is mixed instead of nitrogen, a gas-liquid mixed solution having a purification function in which ozone is contained in bubbles can be generated.

[Gas volume]
The amount of gas present as bubbles in the gas-liquid mixture using pure water as the liquid and various gases as the gas was measured by the following method.
(1) Various ozone-containing gases were mixed with pure water having a conductivity of 0.1 μS / cm at 25 ° C. to obtain a gas-liquid mixture.
(2) In order to separate large bubbles having a diameter of 1 μm or more from water, the gas-liquid mixture was allowed to stand at 25 ° C. for 1 day. As for the standing time, from the Stokes' law, the bubble rising speed: V = d ² × g / (18 × γ)
(D: bubble diameter, g: gravitational acceleration, γ: kinematic viscosity coefficient)
From this equation, the rate of rise of bubbles of 1 μm is about 2.4 × 10 ⁻⁴ m / s. For example, if the water depth of the container at the time of standing is 50 mm, Bubbles can be removed.
(3) The mass of the gas-liquid mixture was measured with an analytical balance having a minimum measured value of 1 mg.
(4) A gas-liquid mixture and a stirrer of a stirrer are placed in a PE + nylon resin vinyl bag with low gas permeability and moisture permeability, and the vinyl bag is sealed with a sealer in a state where there is no air in the bag. .
(5) Immediately after sealing, the mass of the vinyl bag in which the gas-liquid mixture was sealed was measured with an analytical balance.
(6) The vinyl bag in which the gas / liquid mixture at 25 ° C. was sealed by a hot stirrer was heated to 45 ° C., and the gas / liquid mixture was stirred for about 5 hours. By this temperature rise and stirring, fine bubbles and gas dissolved at a saturated dissolution concentration of 45 ° C. or higher were separated from the gas-liquid mixture and collected on the top of the vinyl bag.
(7) The set temperature of the hot stirrer was set to 25 ° C. at room temperature of 25 ° C., and the mixture was stirred for several hours so as to become a liquid having a saturation solubility of 25 ° C.
(8) Using an analytical balance, the mass of the vinyl bag in which gas and liquid were enclosed was measured.
(9) The mass of the gas-liquid mixture and the amount of change in the mass of the liquid caused by the buoyancy caused by the gas separated from the gas-liquid mixture by heating and stirring were obtained from three mass measurements. The mass change amount is the same as the mass of air having the same volume as the gas volume separated from the gas-liquid mixture, and the volume and mass of the separated gas can be calculated from this value.

  FIG. 13 is a graph showing the gas volume measured in this way. The lower region of each bar graph is the amount of gas that was present as the measured bubble, and the upper region is the saturated amount of gas that follows Henry's law. As shown in the graph, the amount of gas contained in the gas-liquid mixture with respect to the saturated dissolution amount was 36 times for nitrogen, 16 times for argon, and 1.9 times for carbon dioxide. If ozone is used instead of various gases, ozone exceeding the supersaturated amount can be present in water. As described above, the gas-liquid mixed liquid can hold the ozone-containing gas in the liquid at a high concentration equal to or higher than the saturated dissolution concentration, and the gas-liquid mixed liquid containing ozone at the high concentration is used for purification. Is something that can be done.

[Bubble size]
A gas-liquid mixture produced in the same manner as above was instantly frozen, cleaved with a cutter in a vacuum, and methane / ethylene flowed through the fractured surface to discharge, producing a hydrocarbon film (replica film) with transferred irregularities. . A conductive osmium thin film was applied to the replica film, dried sufficiently, and observed with a scanning electron microscope (SEM).

  FIG. 14 is an example of a photograph observed by SEM for a gas-liquid mixture of nitrogen and pure water similar to the above. Similarly, by observing a photograph, it was confirmed that when nitrogen, argon, or carbon dioxide was used as the gas, the bubble size of the gas-liquid mixture was 100 nm in diameter distribution peak. The bubbles in the gas-liquid mixture of the above gas and pure water could not be accurately detected by a particle size distribution measuring apparatus such as a dynamic scattering method using a laser. It can be estimated that the same bubble size is obtained when ozone is mixed with the above gas.

[Internal pressure of bubbles]
The pressure inside the bubbles was calculated from the total amount of gas in the gas-liquid mixture. Table 1 shows the total amount of gas and the internal pressure of bubbles calculated from the total amount of gas in a gas-liquid mixture of nitrogen or argon and 25 ° C. pure water.

The internal pressure of the gas in the bubbles is calculated by the following method.
The equation of state of gas is
PV / T = (const)
(P: internal pressure, V: volume, T: internal temperature)
When T is constant, PV = (const)
It is represented by

And the volume of bubbles in the gas-liquid mixture can be calculated from the density of the gas-liquid mixture,
The relationship of atmospheric pressure × total gas volume = bubble internal pressure × total gas volume in liquid is established, and the internal gas pressure in the bubbles is calculated by applying the above measured gas amount to this relational expression. The pressure value is as follows.

For example, when the gas is ozone-containing nitrogen,
Assuming that the volume of water in 1 liter of gas-liquid mixture is w1 liter and the volume of gas in water is w2 liter,
The following relational expression holds for the volume.

w1 + w2 = 1 liter (Formula A)
In addition, the following relational expression holds for the mass.

w1 × density of water + w2 ÷ 22.4 (liter) × 28 (molecular weight) = measured mass (Formula B)
Water density: 997.1g / L for pure water at normal temperature and pressure
22.4 liters: volume of 1 mol of gas Measured mass: 988.3 as shown in Table 1
Solving the above two equations (Equations A and B),
Since w2 = 8.84 × 10 ^ (-3) is calculated,
Internal pressure of gas = atmospheric pressure x total volume of gas ÷ total volume of gas in liquid
= 0.1 x (value in Table 1) / w2
= 0.1 × 0.56 ÷ (8.84 × 10 ^ (-3))
= 6.3 MPa
It becomes.

  In the above calculation, it was assumed that the internal temperature of the bubble was constant (normal temperature), but the actual internal temperature of the bubble is also expected to be higher than the atmospheric temperature (normal temperature). It can be predicted from the gas state equation that the pressure is higher than the above calculation result.

  By the way, in general, the internal pressure of bubbles is calculated as follows. The bubbles are pressurized by the interfacial tension between the gas-liquid interface, and this interfacial tension is derived by Young Laplace's equation (the following equation).

ΔP = 2σ / r
(ΔP: rising pressure, σ: surface tension, r: bubble radius)
According to this equation, for example, in the case of a bubble having a diameter of 100 nm, the bubble internal pressure is 3 MPa.

  On the other hand, the internal pressure in the gas-liquid mixed liquid is 6.3 MPa in the case of nitrogen, for example, as shown in Table 1. In this gas-liquid mixed liquid, bubbles having a diameter of 100 nm are dispersed as shown in the SEM photograph. Therefore, it was confirmed that the bubbles of the gas-liquid mixture had an internal pressure that was about twice or more the value calculated from the Young Laplace equation. Therefore, it was concluded that a stronger interface structure was formed at the bubble interface in the gas-liquid mixture. If ozone is mixed into the bubbles having the strong interface structure, a gas-liquid mixed solution that exhibits purification performance is obtained.

FIG. 15 is a conceptual explanatory diagram illustrating a mechanism by which bubbles in the gas-liquid mixture are stabilized. As shown in the figure, the interface between the bubble B of the ozone-containing gas and the liquid Lq is protected by a strong water molecule such as ice or hydrate whose hydrogen bond distance is shorter than usual, thereby protecting the film structure (crystal structure). It is considered that the film N is formed, the mass transfer between the gas and liquid is prevented, and the bubbles are in a stable state. The internal pressure of bubbles (nanobubbles) in the gas-liquid mixture of ozone-containing nitrogen or ozone-containing argon is about twice or more than the pressure obtained from the Young Laplace equation. As described above, the hydrogen bonding distance at the bubble interface is short and the internal pressure of the bubble is increased, so that a gas-liquid mixture in which bubbles containing ozone are stably present is obtained.

[Bubble distribution]
The amount (number) of bubbles in the gas-liquid mixture was calculated from Table 1.

When the gas is nitrogen, the total amount of bubbles returned to the atmosphere (0.1 MPa) is 0.56 L, and the internal pressure of the bubbles is 6.3 MPa. Therefore, the total volume V1 of bubbles in water is assumed to change isothermally, PV From = const
V1 = 0.56 × 0.1 ÷ 6.3
It becomes.

Since the bubbles are spheres with a radius r = 50 nm, the volume V2 per bubble is
V2 = 4/3 × π × r ^ 3
It becomes.

  From the above, the number of bubbles per liter of water n = V1 ÷ V2 = 1.7 × 10 ^ 16 is calculated.

  Similarly, the number of bubbles per liter of water is calculated as 1.7 × 10 ^ 16 when the gas is argon. Further, when ozone is mixed with nitrogen, it is considered that the number is almost the same.

[Stability]
FIG. 16 shows the supersaturation as the ratio of gas abundance in the gas-liquid mixture with respect to the saturated dissolution concentration when the gas-liquid mixture produced by mixing air with pure water is sealed in a glass bottle and stored at a constant temperature. It is a graph to display. From the graph, it can be seen that the supersaturation level is 6 even after 400 hours and has hardly changed. Therefore, it was confirmed that the bubbles in the gas-liquid mixed liquid exist stably. Moreover, it is thought that the gas-liquid liquid mixture containing ozone is similarly stable.

[Example 2]
Using two kinds of solutions of sodium hypochlorite and water and a gas-liquid mixture of air and water containing ozone, Fe ²⁺ in water was oxidized and precipitated as ferric hydroxide. The initial chlorine concentration of water chlorinated with sodium hypochlorite was 10 mg / L. The initial value of the ozone dissolution concentration of the gas-liquid mixture of air and water containing ozone was 0.2 mg / L. Both solutions were produced at 25 ° C. Chlorine concentration and ozone concentration were measured with a spectrophotometer.

As shown in the graph of FIG. 17, the Fe ²⁺ concentration of water chlorinated with sodium hypochlorite was 0.78 mg / L at the beginning, but gradually decreased with time, and 0.1 mg / L in 65 minutes. It dropped to. On the other hand, the Fe ²⁺ concentration of the gas-liquid mixture of air and water containing ozone decreased with time, but the effect of precipitation was low compared to water chlorinated with sodium hypochlorite. The dissolved ozone causes an oxidation reaction to precipitate iron, but it is considered that the ozone in the nanobubbles could not be effectively utilized only by the reaction with the dissolved ozone.

Therefore, it was found that the mixture of air and water containing ozone was heated to 45 ° C., and the nanobubbles were collapsed to instantly maximize the oxidation treatment. As shown in the graph of FIG. 17, when the temperature was increased from 25 ° C. to 45 ° C. at an elapsed time of 23 minutes (point of arrow a), the Fe ²⁺ concentration rapidly decreased and iron could be deposited.

A Purification device S Gas-liquid mixture generation part M Ozone dissolution part Lq Liquid 1 Pressurization part

Claims (8)

  A gas-liquid mixture generating unit that generates a gas-liquid mixed liquid in which ozone-containing gas is converted into nano-sized bubbles and mixed with the impurity-containing liquid, and a gas-liquid mixed liquid generated by the gas-liquid mixed liquid generating unit An ozone-dissolving unit that breaks down bubbles and dissolves ozone in the impurity-containing liquid, and the gas-liquid mixed liquid generation unit is configured to saturate the liquid of the impurity-containing liquid. A purification apparatus comprising a pressurizing unit that pressurizes and supplies a gas containing ozone to an impurity-containing liquid so as to have a dissolution concentration or higher.   That the ozone dissolving part dissolves ozone in the impurity-containing liquid by collapsing the bubbles of the gas-liquid mixture using at least one of heating, ultrasonic waves, microwaves, and stirring. The purification apparatus according to claim 1, wherein   By pressurizing and mixing the ozone-containing gas into the impurity-containing liquid so as to be nano-sized bubbles, a gas-liquid mixed liquid in which the gas concentration is equal to or higher than the saturated dissolution concentration of the liquid of the impurity-containing liquid is generated, A purification method characterized by donating dissolved ozone to impurities in an impurity-containing liquid by disrupting bubbles in the gas-liquid mixed liquid and dissolving ozone in the impurity-containing liquid.   4. The method according to claim 3, wherein at least one of heating, ultrasonic waves, microwaves, and agitation is used to disintegrate the bubbles in the gas-liquid mixture and dissolve ozone in the impurity-containing liquid. The purification method described.   The purification method according to claim 3 or 4, wherein the liquid of the impurity-containing liquid is water.   The gas-liquid mixture has bubbles in a liquid composed of molecules that form hydrogen bonds, and the hydrogen bond distance of the molecules present at the interface with the liquid bubbles is such that the liquid is at normal temperature and pressure. The purification method according to claim 3, wherein the purification method is shorter than a hydrogen bond distance at a certain time.   4. The liquid of the impurity-containing liquid is a liquid composed of molecules having at least one of an O—H bond, an N—H bond, a (halogen) —H bond, and an S—H bond. The purification method according to any one of items 1 to 6. The pressure of the gas which forms the bubble of a gas-liquid liquid mixture is a pressure higher than the internal pressure of the bubble given by the following Young Laplace's formula | equation, The any one of Claim 3 thru | or 7 characterized by the above-mentioned. Purification method.
Young Laplace's formula ΔP = 2σ / r
[ΔP: rising pressure inside the bubble, σ: surface tension, r: bubble radius]